CN107286607A

CN107286607A - A kind of method for preparing the alternating stratiform Biodegradable high molecular barrier material for having excellent vapor and oxygen barrier property concurrently

Info

Publication number: CN107286607A
Application number: CN201710402598.0A
Authority: CN
Inventors: 郭少云; 韩艾纯; 陈蓉
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2017-06-01
Filing date: 2017-06-01
Publication date: 2017-10-24
Anticipated expiration: 2037-06-01
Also published as: CN107286607B

Abstract

The present invention is to prepare a kind of method for the alternating stratiform Biodegradable high molecular barrier material for having excellent vapor and oxygen barrier property concurrently, its to the effect that by into vapor water barriers layer addition lyophobic dust improve vapor water barriers performance and barrier property and add the diffusion path of the big filler increase oxygen of specific surface area to the stability of humidity, into oxygen barrier layer and improve oxygen barrier property；It is vapor water barriers layer, internal oxygen barrier layer and the sandwich construction that is alternately arranged of vapor water barriers layer using system design outermost layer is coextruded, so as to obtain the stability of excellent vapor and oxygen barrier property and barrier to humidity simultaneously；And optimize the size and morphosis of dispersed phase and filler by the stretching during co-extrusion, shearing force field and further improve barrier property, and mechanical property is improved simultaneously.This method is a kind of continuous flow procedure, and technique is simple, and the product quality indicator between different batches is stable, can large-scale industrial production, it is significant in terms of composite theory research and application and development with wide industrialization and market prospects.

Description

It is a kind of to prepare the alternating biostromal drop for having excellent vapor and oxygen barrier property concurrently The method for solving macromolecule barrier material

Technical field

The present invention relates to a kind of alternating stratiform Biodegradable high molecular resistance for having excellent vapor and oxygen barrier property concurrently The preparation method of barrier material, more particularly to a kind of morphosis controllable, oxygen and vapor water barriers performance it is excellent, Barrier property is not influenceed by ambient humidity change, the alternating stratiform Biodegradable high molecular barrier material of good mechanical performance is made Preparation Method, is related to technical field of composite materials.

Background technology

Biodegradation material is a kind of from extensive renewable resource, and degraded is easy to not under natural environment after use Environment can be polluted, become and substitute the preferred of conventional petroleum base plastics.Because it has good biocompatibility, nothing Toxicity, wide material sources are widely used in the fields such as food, electronic device as packaging material.Have simultaneously to vapor and The excellent barriering effect of oxygen just turns into the important indicator for investigating biodegradation material barrier property.

Vapor and oxygen obstruction ability and its molecular structure are closely related.Some existing biodegradation materials such as synthesize life Thing degraded macromolecular material strand is soft and close-packed arrays, molecular polarity are relatively low, to vapor water barriers performance preferably, but It is relatively low just because of its polarity, it is typically poor to the barrier property of oxygen；Other biodegradation materials such as natural biological is degraded High polymer material due to typically preferable containing polar group or its oxygen barrier property of molecule hydrogen bond, but its polar group often with Water vapour molecule have strong interaction and saboteur's hydrogen bond and in such material rapid osmotic, cause to vapor Barrier property is poor and barrier property is significantly reduced in the case of ambient humidity is elevated, and these factors limit biodegradation Extensive use of the material in fields such as packagings.Research has the Biodegradable high molecular material of good vapor and oxygen barrier property concurrently Material is just particularly important, and many researchers have carried out different study on the modification.

Tradition is used as dispersed phase by adding lyophobic dust or the excellent filler of barrier property, to regulate and control osmoticum Solvability or diffusion path in the material, and then improve the barrier property of biodegradation material.For example, C. Swapna Joseph [1] et al. is mixed in the chitosan that casting normal direction water vapor barrier property can be poor using solution and be with the addition of hydrophobic gather Caprolactone, reduction vapor solubility in the composite and vapor water barriers performance is improved 31%, but also cause simultaneously The oxygen barrier property of composite have dropped 95%.Hua-Dong Huang [2] et al. are prepared using solution mixing casting technique Graphene oxide（GO）/ PVA laminated film, the graphene oxide with good barrier ability causes osmoticum in material Internal diffusion path increases and greatly improves oxygen barrier property, and the GO of addition 0.72% causes the oxygen obstruction of composite Performance improves 87 times, but vapor water barriers performance only improves 3 times.Christian Aulin [3] et al. are poured using solution blending Casting is prepared for nanofiber fiber element-vermiculite Composite, the high-specific surface area of vermiculite（2500 m²/g）Water steaming can be increased Gas effectively improves the barrier property of oxygen and vapor in the diffusion path of material internal simultaneously, but this composite Oxygen and vapor water barriers performance have dropped 21 times and 30 times or so when ambient humidity increases to 80% by 50% respectively, show Shortcoming of the barrier property to ambient humidity less stable.

These researchs show to be difficult to while the barrier property of raising vapor and oxygen, is especially difficult to by being simply blended Ensure the stability of oxygen and vapor water barriers performance to ambient humidity.So, by designing composite morphosis especially It is design sandwich construction to reach while improving the vapor and oxygen barrier property of biodegradation material and ensureing barrier property To the stability of ambient humidity, the just extensive concern by increasing researcher and research.

Jong-Whan Rhim [4] et al. utilize solution casting method by the good agar/card of hydrophily height, oxygen barrier property It is that PLA, internal layer are blending to draw glue blend and hydrophobicity is higher, vapor water barriers performance is good PLA to be prepared into outer layer 3 layer materials of thing, this multilayer material vapor water barriers performance compared with agar/carragheen blend improves 95%, oxygen obstruction Performance improves 94%.Federico Carosio [5] et al. are introduced on PLA surface using solution laminated assembling technology and alternately arranged Cheating engaging layer in Nafion layers of the cheating engaging layer and hydrophobicity of row, this alternating multilayered structure can be effectively increased oxygen and water The diffusion path of steam and improve multilayer material to oxygen and the barrier property of vapor, Nafion layers of hydrophobicity effectively improves many The hydrophobicity of layer material and make it that multilayer material also possesses good oxygen and vapor water barriers performance under high humidity environment, i.e., Barrier property is improved to the stability of humidity.

Though these methods can improve material simultaneously to vapor and the barrier property of oxygen, its preparation is entered in the solution OK, the number of plies and Rotating fields design are difficult to flexible Effective Regulation, and preparation technology is complicated, and solvent removes difficult, it is difficult to continuous scale Metaplasia is produced.To solve this problem, to the controlled material Rotating fields during being processed and formed at one time, realization has excellent water steaming concurrently The preparation of the alternating stratiform biological degradable composite material of gas and oxygen barrier property is particularly important.Design sandwich construction is simultaneously obtained Excellent barrier properties are obtained, realize that the raising of monolayer material barrier property and the good compounding of different barrier properties are crucial.How Compounded using component and the barrier property of monolayer material is respectively increased, designed by moulding process and regulate and control Rotating fields and had concurrently with reaching The problem of Biodegradable high molecular composite of excellent vapor and oxygen barrier property is in the urgent need to address at this stage.

Bibliography

[1]Swapna Joseph C, Harish Prashanth KV, Rastogi NK, Indiramma AR, Yella Reddy S, Raghavarao KSMS. Optimum blend of chitosan and Poly-(ε-caprolactone) for fabrication of films for food packaging applications. FOOD BIOPROCESS TECH. 2009, 4:1179-85.

[2]Huang H-D, Ren P-G, Chen J, Zhang W-Q, Ji X, Li Z-M. High barrier graphene oxide nanosheet/poly(vinyl alcohol) nanocomposite films. J Membr Sci. 2012,409-410:156-63.

[3]Aulin C, Salazar-Alvarez G, Lindstrom T. High strength, flexible and transparent nanofibrillated cellulose-nanoclay biohybrid films with tunable oxygen and water vapor permeability, Nanoscale, 2012, 4: 6622-6628.

[4] Jong-Whan Rhim. Effect of PLA lamination on performance characteristics of agar/κ-carrageenan/clay bio-nanocomposite film, Food Research International, 2013, 51: 714–722.

[5]Federico Carosio, Samuele Colonna, Alberto Fina, Gaulthier Rydzek, Joseph Hemmerle, Loïc Jierry, Pierre Schaaf, and Fouzia Boulmedais. Efficient gas and water vapor barrier properties of thin Poly(lactic acid) packaging films: Functionalization with moisture resistant Nafion and clay multilayers, Chem. Mater, 2014, 26: 5459−5466。

The content of the invention

The shortcoming of excellent vapor and oxygen barrier property can not be had concurrently simultaneously for Biodegradable material and existing Some solwution methods prepare the deficiency of laminated insulations composite, and the purpose of the present invention is directed to a kind of melting co-extrusion for form Structure is adjustable, have excellent vapor concurrently and oxygen barrier property, barrier property do not influenceed by ambient humidity change, mechanical property it is good The method of good alternating stratiform Biodegradable high molecular barrier material, this method can one-shot forming prepare oxygen and vapor water barriers The barrier material that performance is improved simultaneously, the excellent in stability that its barrier property changes to humidity, and mechanical property are improved simultaneously.Should Method can be continuously produced simultaneously, process simplicity, steady quality, suitable large-scale industrial production.

The general principle of the present invention is to select suitable biodegradated polymer materal with hydrophobic dispersion mutually as biology Degraded macromolecular base vapor water barriers layer, biodegradated polymer materal and laminal filter are used as Biodegradable high molecular base oxygen Barrier layer, and it is vapor water barriers layer, internal steam barrier layer and oxygen to prepare by way of multilayer extrusion two layers of outermost The parallel multilayer material being arranged alternately of barrier layer, outermost layer vapor water barriers layer can protect the barrier property of composite not by wet Degree influence；The tensile shear field of force regulation vapor water barriers layer and the form of oxygen barrier layer during multilayer extrusion are utilized simultaneously Structure distribution, further improves individual layer vapor and oxygen barrier property, can so obtain and have excellent vapor and oxygen concurrently The alternating stratiform Biodegradable high molecular barrier material of barrier property.

The present invention selects the material insensitive to vapor in vapor water barriers layer choosing and makees matrix, hydrophobicity from this point Ester type compound makees dispersed phase, is remarkably improved the hydrophobicity of vapor water barriers layer, and reduction penetrates into the vapor of material internal Content simultaneously increases diffusion path of the vapor this layer of inside, thus improves the barrier property of vapor and keeps vapor water barriers Performance does not change with ambient humidity；The biodegradation material good to oxygen barrier property is selected to make matrix in oxygen barrier layer, profit Increase diffusion path of the oxygen in this layer with the filler that specific surface area is big and barrier property is excellent, thus further improving should Barrier property of the layer to oxygen；And oxygen barrier layer and vapor water barriers layer effectively overlapping are made and good using multi-layer co-extruded device Good compounding, makes composite have good vapor and oxygen barrier property concurrently；Design Rotating fields make outermost layer be vapor water barriers Layer, can protect internal layer oxygen barrier layer not influenceed by vapor and ambient humidity, material block performance is not increased with ambient humidity Plus and decline.

Specifically, the present invention is to be added to water steaming by selecting one kind that there is good hydrophobic material to be used as dispersed phase Vapor water barriers layer is prepared in the good biodegradated polymer materal of vapour lock separating performance, using hydrophobic dispersion inside it Form the water vapor diffusion path of growth to reduce water vapor diffusion coefficient, and put forward the hydrophobicity of this layer, make vapor be difficult to ooze Penetrate into the stronger vapor water barriers layer inside of hydrophobicity and significantly reduce swelling action of the vapor to material, make it in DIFFERENT WET Spending under environment keeps barrier property stable, is derived from the good vapor water barriers layer of barrier property, and its barrier property has Good humidity stability.And by selecting the laminal filter that specific surface area is big, barrier property is excellent to be added to oxygen-barrier property Oxygen barrier layer is prepared in biodegradated polymer materal that can be excellent, makes filler dispersed in this layer of matrix and effectively shells From and form the oxygen diffusion path increased and improve oxygen barrier property, be derived from the good oxygen obstruction of barrier property Layer.It is then vapor water barriers layer, internal oxygen barrier layer and vapor water barriers by two layers of multilayer extrusion system and arranging outermost The sandwich construction that layer is arranged alternately, you can while improving the vapor and oxygen barrier property of material, and utilize vapor water barriers Layer, which is reduced, to be penetrated into the vapor of material internal to protect the oxygen barrier layer of inside not influenceed by vapor and humidity, and then Improve stability of the barrier property to humidity of barrier material.While by means of layer multiplier multiple during multilayer extrusion Shearing, stretching action during stratiform overlapping strongly make the filler stripping in dispersed phase deformation, oxygen barrier layer in vapor water barriers layer From and increase the specific surface area of dispersed phase and filler, and the effect by flowing the field of force make they parallel to material surface be orientated, So as to further barrier of the increase osmoticum in the constantly improve material of the diffusion path of material internal to oxygen and vapor Ability.The final alternating stratiform Biodegradable high molecular barrier material that can obtain with excellent vapor and oxygen barrier property Material, while the mechanical property of composite is also improved.

The present invention is based on above-mentioned principle, realizes that the technical scheme that foregoing invention purpose is used is：By biodegradable high score Subbase vapor water barriers layer material and Biodegradable high molecular base oxygen barrier layer material through fusion plastification, are squeezed by two respectively Go out the compound coextrusion system of machine to overlap in the junction station for being designed to 3 runners after the initial configuration for obtaining 3 layers of parallel arrangement, Stratiform overlapping is carried out by n layer multiplier being connected with the junction station again, being formed, there is Biodegradable high molecular Ji Shui to steam The sandwich construction extrudate that vapour lock interlayer and Biodegradable high molecular base oxygen barrier layer are arranged alternately：

（1）Described Biodegradable high molecular base vapor water barriers layer material be melt-processable, hydrophilic contact angle 60 °~ Between 90 °, vapor permeability be less than 3E-13 gcmcm^-2·s^-1·Pa^-1（90%RH）Biodegradated polymer materal （The matrix of vapor water barriers layer）And the hydrophobic biological degraded ester of melt-processable, hydrophilic contact angle between 90 °~150 ° Class compound（The dispersed phase of vapor water barriers layer）It is 50~99% by weight percentage：50~1% carry out the blend of dispensing；

（2）Described Biodegradable high molecular base oxygen barrier layer material is that strand is small containing polar functional group, oxygen permeability In 2E-16 cm³·cm/cm²·s·Pa（0%RH）And the biodegradated polymer materal of melt-processable（Oxygen barrier layer Matrix）With specific surface area in 50-3000 m²Laminal filter between/g（The filler of oxygen barrier layer）It is 50 by weight percentage ~99%：50~1% carry out the blend of dispensing.

During the above-mentioned multiple stratiform overlapping effect by n layer multiplier being connected with junction station, preparation side Method using the applicant apply Chinese patent CN101439576A disclosed in by extruder（A、B）, junction station（C）, layer times Increase device（D）With shaping mouth mold（E）The microbedding co-extruder of composition, is characterized in first preparing biodegradable vapor water barriers layer respectively Material and biodegradable oxygen barrier layer material, dispersed phase or filler in barrier layer are regulated and controled in the base by melt blending Dispersing morphology improves barrier layer to vapor or the obstructing capacity of oxygen, then by biodegradable vapor water barriers layer material and life Thing degraded oxygen barrier layer material puts into the two extruderses of microbedding co-extrusion device respectively（A、B）In, via junction station（C）It is folded It is combined into after the initial configuration of 3 layers of parallel arrangement by n layer multiplier（D）The stratified material being arranged alternately is overlapped into, in layer times Increase barrier layer material in device be stretched shear action and make dispersed phase in barrier layer and filler deformation and regulate and control dispersed phase and Appearance structure, specific surface area size and the orientation of filler, further improve barrier layer to vapor, the barrier property of oxygen and resistance Separating performance is to the stability of ambient humidity, then from shaping mouth mold（E）Middle extrusion obtains 2 through cooling tractor traction sizing^（n ^+1）+ 1 layer of outermost layer is alternately arranged sandwich construction for vapor water barriers layer, internal oxygen barrier layer and vapor permeating layers barrier layer and squeezed Go out thing.

Biodegradable vapor water barriers layer and biodegradable oxygen are thus realized by the method for simple melt-processed The Rotating fields of barrier layer are constructed, and by regulating and controlling the morphosis of barrier layer, improve constantly barrier layer to vapor and oxygen Barrier property, realizes the stability for having both excellent vapor and oxygen barrier property and barrier property simultaneously to humidity, and in fact Existing mechanical property is synchronously improved.This new preparation has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable On the one hand the method for macromolecule barrier material can effectively improve the vapor and oxygen blocking of biodegradated polymer materal simultaneously Separating performance, another aspect process simplicity, steady quality and suitable large-scale industrial production, can avoid making for solvent With, fundamentally solve solvent and be difficult to handle, the problems such as polluting environment.

The matrix of Biodegradable high molecular base vapor water barriers layer in above-mentioned technical proposal is selected from polycaprolactone, poly- breast One kind in acid, poly-succinic fourth diester, polyhydroxyalkanoate, PHBV；Vapor hinders The dispersed phase of interlayer is selected from glyceryl tristearate, laurin, single nutmeg acid glyceride, three myristic acid glycerine One kind in ester, tripalmitin.

Compare water in the hydrophilic contact angle of the dispersed phase of Biodegradable high molecular base vapor water barriers layer in above-mentioned technical proposal The hydrophilic contact angle of the matrix of vapor barrier layer is high more than 30 °.

The mode for preparing Biodegradable high molecular base vapor water barriers layer material in above-mentioned technical proposal is by the layer Matrix and dispersed phase high mixer mix.

The mode for preparing Biodegradable high molecular base vapor water barriers layer material in above-mentioned technical proposal can also be by Matrix and dispersed phase in this layer carry out melting mixing in an extruder.

The mode for preparing Biodegradable high molecular base vapor water barriers layer material in above-mentioned technical proposal can also be by Matrix and dispersed phase in this layer is first in high mixer mixing, then carry out melting mixing in an extruder.

The matrix of Biodegradable high molecular base oxygen barrier layer in above-mentioned technical proposal is selected from polyvinyl alcohol, thermoplastic starch One kind in powder, thermoplasticity soybean protein isolate；The filler of oxygen barrier layer is in montmorillonite, graphene, vermiculite, zeolite It is a kind of.

The mode for preparing Biodegradable high molecular base oxygen barrier layer material in above-mentioned technical proposal is by this layer Matrix and dispersed phase are mixed in high mixer.

The mode for preparing Biodegradable high molecular base oxygen barrier layer material in above-mentioned technical proposal can also be by this Matrix and dispersed phase in layer carry out melting mixing in an extruder.

The mode for preparing Biodegradable high molecular base oxygen barrier layer material in above-mentioned technical proposal can also be by this Matrix and dispersed phase in layer is first in high mixer mixing, then carry out melting mixing in an extruder.

Sandwich construction extrudate in above-mentioned technical proposal is by by two extruderses（A、B）, junction station（C）, n layer Multiplier（D）, shaping mouth mold（E）And cooling tractor（F）The multilayer extrusion system melt extrusion and cooling and shaping of composition are obtained Arrive；By the Thickness ratio of the gross thickness, internal total number of plies, vapor water barriers layer and the oxygen barrier layer that regulate and control sandwich construction extrudate Vapor water barriers performance and oxygen barrier property can be regulated and controled.

Sandwich construction extrudate gross thickness in above-mentioned technical proposal is 0.01-10mm；The inside of sandwich construction extrudate Total number of plies is 3-32769；The thickness ratio of biodegradable vapor water barriers layer and biodegradable oxygen barrier layer is 1:99-99:1.

3 layers of initial configuration of the sandwich construction extrudate in above-mentioned technical proposal are that two outer layers are vapor water barriers layer, Intermediate layer is oxygen barrier layer, when using n layer multiplier, and material is vapor water barriers layer in two layers of two outermosts, interior Portion's vapor water barriers layer structure being arranged alternately parallel with oxygen barrier layer, the total number of plies of material is 2^（n+1）+ 1 layer, wherein, n is 0- 14。

It is of the invention compared with the method that existing solwution method prepares vapor and oxygen multilayer barrier material, summed up Advantage following prominent：

1st, the present invention chooses hydrophobicity and degrades ester type compound as dispersed phase, by its biology good with vapor water barriers performance The effective compounding of degraded macromolecular material prepares vapor water barriers layer, and the lyophobic dust used can be existed with Effective Regulation vapor The diffusion path of material internal and improve vapor water barriers performance, and the hydrophobicity of material can be improved and make material in different humidity Good vapor water barriers performance is respectively provided with environment.

2nd, the excellent filler of present invention selection high-specific surface area, barrier property is added to the excellent biology of oxygen barrier property Oxygen barrier layer is prepared in degraded macromolecular material, the filler of the high-specific surface area used can be effectively increased oxygen in the layer The diffusion path in portion and significantly improve oxygen barrier property.

3rd, the present invention can once prepare shaping using multi-layer co-extruded system and well have vapor and oxygen barrier property concurrently Alternating stratiform Biodegradable high molecular barrier material, and can Effective Regulation Rotating fields, pass through vapor water barriers layer and oxygen blocking The alternating superposition of interlayer and effectively compounding, while improving composite vapor water barriers performance and oxygen barrier property, and pass through Rotating fields design makes material block performance good to humidity stability, so as to obtain good vapor and oxygen barrier property While its barrier property is not influenceed by ambient humidity.

4th, the cuniform channel of middle level multiplier of the present invention can regulate and control dispersed phase and filler size, improve phase morphology, make point Dephasing and packing specific area increase and it is orientated parallel to material surface, vapor and oxygen barrier property is further carried It is high；And Biodegradable high molecular substrate molecule chain orientation is made by the field of force of shearing, stretching and mechanical property is improved, having height concurrently The raising of mechanical property is realized while vapor and oxygen barrier property.

5th, the preparation method is a kind of continuous flow procedure, is conducive to the raising of production efficiency；Technique is simple, different batches Between product quality indicator it is stable, can large-scale industrial production, have a wide range of application, before wide industrialization and market Scape；Realize polymeric articles high performance and functionalization is same, improve the surcharge of polymeric articles, widen polymerization The application of produce product, it is significant in terms of composite theory research and application and development.

Brief description of the drawings

The present invention is further illustrated below in conjunction with the accompanying drawings.

Fig. 1 is the structural representation of microbedding co-extruder involved in the present invention：A, B are extruder；C is junction station；D is Layer multiplier；E is cooling tractor.

Fig. 2 is to have the biodegradable high score of the alternating stratiform of excellent vapor and oxygen barrier property concurrently prepared by the present invention The structure enlarged diagram of sub- barrier material.In figure, F：Vapor water barriers layer, G：Oxygen barrier layer.

Specific implementation method：

The present invention is further described specifically by the following examples.In following embodiment, the consumption of each component It is quality consumption.Be necessary it is pointed out here that, example below simply the present invention is further illustrated, it is impossible to be interpreted as to The limitation of invention protection domain, person skilled in art can carry out some non-according to the invention described above content to the present invention The modifications and adaptations of matter.

Embodiment 1

The first step, Biodegradable high molecular base vapor water barriers layer（Hereinafter referred to as vapor water barriers layer）It is water from polycaprolactone Vapor barrier layer matrix, glyceryl tristearate is vapor water barriers layer dispersed phase；Biodegradable high molecular base oxygen barrier layer （Hereinafter referred to as oxygen barrier layer）From polyvinyl alcohol be oxygen barrier layer matrix, montmorillonite be oxygen barrier layer filler, by with Lower component and part is got the raw materials ready：

Vapor water barriers layer component parts by weight

Polycaprolactone (for vapor water barriers layer matrix) 80

Glyceryl tristearate (for vapor water barriers layer dispersed phase) 20

Oxygen barrier layer composition weight number

Polyvinyl alcohol (being oxygen barrier layer matrix) 90

Montmorillonite (being oxygen barrier layer filler) 10

Second step, is placed in 40 DEG C of vacuum drying ovens by polycaprolactone, glyceryl tristearate and dries 6 hours, polyvinyl alcohol, illiteracy are de- Soil is placed in 80 DEG C of vacuum drying ovens and dried 6 hours；

3rd step, the vapor water barriers layer material and oxygen barrier layer material of the drying that second step is obtained are respectively placed in high mixer Middle premixing 5 minutes, its rotating speed is 100 revs/min, respectively obtains the pre-composition of polycaprolactone and glyceryl tristearate（Water Vapor barrier layer pre-composition）And polyvinyl alcohol and the pre-composition of montmorillonite（Oxygen barrier layer pre-composition）, by vapor water barriers layer Pre-composition 40 DEG C of dryings 3 hours in vacuum drying oven, oxygen barrier layer pre-composition is dried 3 hours at 80 DEG C.

4th step, during the vapor water barriers layer pre-composition and oxygen barrier layer pre-composition that the 3rd step is obtained are dropped in respectively Squeezing by extruder A, B, junction station C, layer multiplier D the microbedding co-extruder constituted disclosed in state patent CN101439576A Go out in machine A and extruder B（See Fig. 1）, regulation extruder A and extruder B rotating ratio is 1:1, pre-composition is by extruder Charge door, transportation section, melt zone, homogenizing zone carry out fusion plastification, then two strands of melts is overlapped into initially by junction station C Structure, is molded, you can it is 33 to obtain total number of plies after the multiple stratiform overlapping of 4 layer multipliers by cooling tractor Layer, wherein vapor water barriers layer（Totally 17 layers）, oxygen barrier layer（Totally 16 layers）Be alternately arranged, width 80mm, thickness 1mm composite wood Material（See Fig. 2）, the Thickness ratio of wherein vapor water barriers layer and oxygen barrier layer is 1:1.Wherein vapor water barriers layer extruder Charge door, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 80 DEG C, 120 DEG C, 150 DEG C, 150 DEG C, 170 DEG C；Oxygen The charge door of barrier layer extruder, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 190 DEG C, 210 DEG C, 220 DEG C, 230℃、230℃；The temperature of junction station and layer multiplier is respectively 230 DEG C and 230 DEG C.

It is above-mentioned many according to being put into after above-mentioned steps and parameter drying, high mixer mixing using above-mentioned vapor water barriers layer proportioning Separate unit extruder in layer co-extrusion device is extruded, but without junction station and layer multiplier, by with multi-layer co-extruded dress Put middle identical extrusion neck ring mold to be cooled and shaped, obtain wide 80mm, thickness 1mm control sample 1.The charging of wherein single extruder Mouth, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 80 DEG C, 120 DEG C, 150 DEG C, 150 DEG C, 170 DEG C.

Dried using above-mentioned oxygen barrier layer proportioning according to above-mentioned steps and parameter, high mixer puts into above-mentioned multilayer after mixing Separate unit extruder in co-extrusion device is extruded, but without junction station and layer multiplier, by with multi-layer co-extruded device Middle identical extrusion neck ring mold is cooled and shaped, and obtains wide 80mm, thickness 1mm control sample 2.The charging of wherein single extruder Mouth, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 190 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C.

Vapor and oxygen permeability, the mechanics of control sample and alternate multiple composite obtained by above-mentioned preparation method Performance is following table.

Vapor permeability under the conditions of the different humidity of table 1.（Unit：E-14 g·cm/cm²·s·Pa）Oozed with oxygen Saturating rate（Unit：E-14 cm³·cm/cm²·s·Pa）

In above-mentioned preparation method, the control sample 1 of the present embodiment（Hereinafter referred to as control sample 1）Vapor water barriers performance relative Humidity is risen to by 50%RH only declines 16% after 90%RH, show that its vapor water barriers performance has good stability to humidity change；But Its oxygen permeability（For 5.1 E-14 cm³·cm/cm²·s·Pa）The resistance of conventional packaging material polyvinylidene chloride than now High two orders of magnitude of separating performance（Polyvinylidene chloride oxygen permeability is 0.057 E-14 cm³·cm/cm²·s·Pa）.This reality Apply the control sample 2 of example（Hereinafter referred to as control sample 2）Oxygen barrier property under 50%RH relative humidity is good, but ought be relatively wet Degree rises to its oxygen barrier property reduction by 96% after 90%RH；And after relative humidity rises to 90%RH by 50%RH, vapor Permeability is by 0.8 E-14 gcm/cm²SPa rises to 35 E-14 gcm/cm²SPa, barrier property is reduced 97.7%, show that the barrier property of control sample 2 changes very sensitive to humidity, barrier property is badly damaged after relative humidity increase.

Vapor water barriers layer and oxygen barrier layer are effectively superimposed by the present embodiment using multi-layer co-extruded system, relative Humidity is risen to after 90%RH by 50%RH, and the vapor and oxygen permeability of embodiment 1 keep stable, vapor permeability by 1.9 E-14 g·cm/cm²SPa, which becomes, turns to 2.3 E-14 gcm/cm²SPa, increase only 0.4 E-14 g cm/cm²·s·Pa；Oxygen permeability is by 0.0045 E-14 cm³·cm/cm²SPa is changed to 0.0065 E-14 cm³·cm/cm²SPa, only rises 0.002 cm³·cm/cm²·s·Pa.Compared with control sample 2, the resistance of embodiment 1 Separating performance is significantly improved to the stability of humidity, and this is due to that the vapor water barriers layer of outer layer can effectively completely cut off vapor and ooze Thoroughly, the oxygen barrier layer inside protection is not influenceed by vapor and humidity, is derived from good barrier property to humidity Stability.The oxygen barrier property of embodiment 1 improves 99.91% compared with control sample 1 when other relative humidity is 50%RH, and Under high humidity（90%RH）Its barrier property also improves 99.90% than control sample 1, during this is due to the present embodiment sandwich construction The excellent oxygen barrier layer of oxygen barrier property is introduced, and oxygen barrier layer is protected from humidity by vapor water barriers layer Influence, so as to effectively improve oxygen barrier property of the multilayer material under high and low relative humidities.So the present embodiment The sandwich construction of use can effectively improve material oxygen and water vapor barrier property, and barrier property is also notable to the stability of humidity Improve.

The mechanical property of table 2.

Meanwhile, the mechanical property of control sample and alternate multiple barrier material is as shown in upper table, and polycaprolactone is soft and tough, poly- second Enol is hard and crisp material.And the modulus of alternate multiple barrier material improves 89%, elongation at break compared with polycaprolactone 96%, i.e. alternate multiple barrier material are improved compared with polyvinyl alcohol can be by the combination of the good mechanical properties of the two one Rise.This is due to the shearing of the multiple stratiform overlapping of layer multiplier, stretching action so that exists in alternate multiple composite and is permitted Multiple solutions, bed boundary compatibility is good, caking property strong, interface interaction power is big, is caused according to stratiform equivalent superposition in parallel The caking property of multilayer materials is constantly lifted, so when being stretched by the external world, interface interaction enables to alternate multiple The mechanical property of barrier material is obviously improved；The shear tension effect in layer multiplier also make it that dispersed phase, filler are thin in addition Change, have more preferable caking property with matrix, while the strand of matrix has an orientation effect and causes mechanical property is further integrated to carry It is high.

As needed, the Thickness ratio and the number of plies in the present embodiment also can adjust to meet different oxygen and vapor water barriers Demand and mechanical property requirements.

Embodiment 2

The first step, Biodegradable high molecular base vapor water barriers layer（Hereinafter referred to as vapor water barriers layer）It is water from polycaprolactone Vapor barrier layer matrix, glyceryl tristearate is vapor water barriers layer dispersed phase；Biodegradable high molecular base oxygen barrier layer (hereinafter referred to as oxygen barrier layer）From polyvinyl alcohol be oxygen barrier layer matrix, montmorillonite be oxygen barrier layer filler, by with Lower component and part is got the raw materials ready：

Vapor water barriers layer component parts by weight

Polycaprolactone (for vapor water barriers layer matrix) 70

Glyceryl tristearate (for vapor water barriers layer dispersed phase) 30

Oxygen barrier layer composition weight number

Polyvinyl alcohol (being oxygen barrier layer matrix) 85

Montmorillonite (being oxygen barrier layer filler) 15

4th step, during the vapor water barriers layer pre-composition and oxygen barrier layer pre-composition that the 3rd step is obtained are dropped in respectively Squeezing by extruder A, B, junction station C, layer multiplier D the microbedding co-extruder constituted disclosed in state patent CN101439576A Go out in machine A and extruder B（See Fig. 1）, regulation extruder A and extruder B rotating ratio is 1:1, pre-composition is by extruder Charge door, transportation section, melt zone, homogenizing zone carry out fusion plastification, then two strands of melts is overlapped into initially by junction station C Structure, is molded, you can it is 33 to obtain total number of plies after the multiple stratiform overlapping of 4 layer multipliers by cooling tractor Layer, wherein vapor water barriers layer（Totally 17 layers）, oxygen barrier layer（Totally 16 layers）Wide 80mm, the thickness 1mm composite wood being alternately arranged Material（See Fig. 2）, the Thickness ratio of wherein vapor water barriers layer and oxygen barrier layer is 1:1.Wherein vapor water barriers layer extruder Charge door, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 80 DEG C, 120 DEG C, 150 DEG C, 150 DEG C, 170 DEG C；Oxygen The charge door of barrier layer extruder, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 190 DEG C, 210 DEG C, 220 DEG C, 230℃、230℃；The temperature of junction station and layer multiplier is respectively 230 DEG C and 230 DEG C.

The vapor and oxygen barrier property of control sample and alternate multiple composite obtained by above-mentioned preparation method, power Performance is following table.

In above-mentioned preparation method, the control sample 1 of the present embodiment（Hereinafter referred to as control sample 1）Vapor water barriers performance in phase Humidity is risen to by 50%RH and only declines 16% after 90%RH, shows that its vapor water barriers performance has good stability to humidity change； But its oxygen permeability（For 4.8 E-14 cm³·cm/cm²·s·Pa）Than now, conventional packaging material polyvinylidene chloride is high Two orders of magnitude（Polyvinylidene chloride oxygen permeability is 0.057 E-14 cm³·cm/cm²·s·Pa）.Pair of the present embodiment Than sample 2（Hereinafter referred to as control sample 2）Oxygen barrier property under 50%RH relative humidity is good, but when relative humidity rises to Its oxygen barrier property reduction by 96.3% after 90%RH；And after relative humidity rises to 90%RH by 50%RH, vapor permeability By 0.7 E-14 gcm/cm²SPa rises to 30 E-14 gcm/cm²SPa, barrier property reduces 97.6%, Show that the barrier property of control sample 2 changes very sensitive to humidity, barrier property is badly damaged after relative humidity increase.

Vapor water barriers layer and oxygen barrier layer are effectively superimposed by the present embodiment using multi-layer co-extruded system, relative Humidity is risen to after 90%RH by 50%RH, and the vapor and oxygen permeability of embodiment 2 keep stable, vapor permeability by 1.6 E-14 g·cm/cm²SPa, which becomes, turns to 2.0 E-14 gcm/cm²SPa, increase only 0.4 E-14 g cm/cm²·s·Pa；Oxygen permeability is by 0.0031 E-14 cm³·cm/cm²SPa is changed to 0.0050 E-14 cm³·cm/cm²SPa, only rises 0.0019 cm³·cm/cm²·s·Pa.Compared with control sample 2, the resistance of embodiment 2 Separating performance is significantly improved to the stability of humidity, and this is due to that the vapor water barriers layer of outer layer can effectively completely cut off vapor and ooze Thoroughly, the oxygen barrier layer inside protection is not influenceed by vapor and humidity, is derived from good barrier property to humidity Stability.The oxygen barrier property of embodiment 2 improves 99.93% compared with control sample 1 when other relative humidity is 50%RH, and Under high humidity（90%RH）Its barrier property also improves 99.92% than control sample 1, during this is due to the present embodiment sandwich construction The excellent oxygen barrier layer of oxygen barrier property is introduced, and oxygen barrier layer is protected from humidity by vapor water barriers layer Influence, so as to effectively improve oxygen barrier property of the multilayer material under high and low relative humidities.So the present embodiment The sandwich construction of use can effectively improve material oxygen and water vapor barrier property, and barrier property is also notable to the stability of humidity Improve.

The mechanical property of table 2.

Meanwhile, the mechanical property of control sample and alternate multiple barrier material is as shown in upper table, and polycaprolactone is soft and tough, poly- second Enol is hard and crisp material.And the modulus of alternate multiple barrier material improves 90%, elongation at break compared with polycaprolactone 95% is improved compared with polyvinyl alcohol, alternate multiple barrier material being capable of being combined together the good mechanical properties of the two. This is due to the shearing of the multiple stratiform overlapping of layer multiplier, stretching action so that there is many in alternate multiple composite Interface, bed boundary compatibility is good, caking property strong, interface interaction power is big, is caused many according to stratiform equivalent superposition in parallel The caking property of layer composite is constantly lifted, so when being stretched by the external world, interface interaction enables to alternate multiple to hinder The mechanical property of barrier material is obviously improved；The shear tension effect in layer multiplier also causes dispersed phase, filler refinement in addition, There is more preferable caking property with matrix, while the strand of matrix has orientation effect and causes mechanical property is further comprehensive to improve.

Embodiment 3

The first step, Biodegradable high molecular base vapor water barriers layer（Hereinafter referred to as vapor water barriers layer）It is water from polycaprolactone Vapor barrier layer matrix, myristin is vapor water barriers layer dispersed phase；Biodegradable high molecular base oxygen obstruction Layer（Hereinafter referred to as oxygen barrier layer）It is oxygen barrier layer matrix from polyvinyl alcohol, montmorillonite is oxygen barrier layer filler, is pressed Following components and parts by weight are got the raw materials ready：

Vapor water barriers layer component parts by weight

Polycaprolactone (for vapor water barriers layer matrix) 80

Myristin (for vapor water barriers layer dispersed phase) 20

Oxygen barrier layer composition weight number

Polyvinyl alcohol (being oxygen barrier layer matrix) 85

Montmorillonite (being oxygen barrier layer filler) 15

Second step, is placed in 40 DEG C of vacuum drying ovens by polycaprolactone, myristin and dries 6 hours, polyvinyl alcohol, illiteracy De- soil is placed in 80 DEG C of vacuum drying ovens and dried 6 hours；

3rd step, the vapor water barriers layer material and oxygen barrier layer material of the drying that second step is obtained are respectively placed in high mixer Middle premixing 5 minutes, its rotating speed is 100 revs/min, respectively obtains the pre-composition of polycaprolactone and myristin （Vapor water barriers layer pre-composition）And polyvinyl alcohol and the pre-composition of montmorillonite（Oxygen barrier layer pre-composition）, by vapor water barriers Layer pre-composition 40 DEG C of drying 3 hours in vacuum drying oven, oxygen barrier layer pre-composition was in 80 DEG C of dryings 3 hours.

4th step, during the vapor water barriers layer pre-composition and oxygen barrier layer pre-composition that the 3rd step is obtained are dropped in respectively Squeezing by extruder A, B, junction station C, layer multiplier D the microbedding co-extruder constituted disclosed in state patent CN101439576A Go out in machine A and extruder B（See Fig. 1）, regulation extruder A and extruder B rotating ratio is 1:1, pre-composition is by extruder Charge door, transportation section, melt zone, homogenizing zone carry out fusion plastification, then two strands of melts is overlapped into initially by junction station C Structure, is molded, you can it is 129 to obtain total number of plies after the multiple stratiform overlapping of 6 layer multipliers by cooling tractor Layer, wherein vapor water barriers layer（Totally 65 layers）, oxygen barrier layer（Totally 64 layers）Wide 80mm, the thickness 1mm composite wood being alternately arranged Material（See Fig. 2）, the Thickness ratio of wherein vapor water barriers layer and oxygen barrier layer is 1:1.Wherein vapor water barriers layer extruder Charge door, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 80 DEG C, 120 DEG C, 150 DEG C, 150 DEG C, 170 DEG C；Oxygen The charge door of barrier layer extruder, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 190 DEG C, 210 DEG C, 220 DEG C, 230℃、230℃；The temperature of junction station and layer multiplier is respectively 230 DEG C and 230 DEG C.

In above-mentioned preparation method, the control sample 1 of the present embodiment（Hereinafter referred to as control sample 1）Vapor water barriers performance in phase Humidity is risen to by 50%RH and only declines 16% after 90%RH, shows that its vapor water barriers performance has good stability to humidity change； But its oxygen permeability（For 5.1 E-14 cm³·cm/cm²·s·Pa）Than now, conventional packaging material polyvinylidene chloride is high Two orders of magnitude（Oxygen permeability is 0.057 E-14 cm³·cm/cm²·s·Pa）.The control sample 2 of the present embodiment（Following letter Claim control sample 2）Oxygen barrier property under 50%RH relative humidity is good, but its oxygen after relative humidity rises to 90%RH Barrier property reduction by 96.3%；And after relative humidity rises to 90%RH by 50%RH, vapor permeability is by 0.7 E-14 g cm/cm²SPa rises to 30 E-14 gcm/cm²SPa, barrier property reduces 97.6%, shows control sample 2 Barrier property changes very sensitive to humidity, and barrier property is badly damaged after relative humidity increase.

Vapor water barriers layer and oxygen barrier layer are effectively superimposed by the present embodiment using multi-layer co-extruded system, relative Humidity is risen to after 90%RH by 50%RH, and the vapor and oxygen permeability of embodiment 3 keep stable, vapor permeability by 1.8 E-14 g·cm/cm²SPa, which becomes, turns to 2.1 E-14 gcm/cm²SPa, increase only 0.3 E-14 g cm/cm²·s·Pa；Oxygen permeability is by 0.0032 E-14 cm³·cm/cm²SPa is changed to 0.0055 E-14 cm³·cm/cm²SPa, only rises 0.0023 cm³·cm/cm²·s·Pa.Compared with control sample 2, the resistance of embodiment 3 Separating performance is significantly improved to the stability of humidity, and this is due to that the vapor water barriers layer of outer layer can effectively completely cut off vapor and ooze Thoroughly, the oxygen barrier layer inside protection is not influenceed by vapor and humidity, is derived from good barrier property to humidity Stability.The oxygen barrier property of embodiment 3 improves 99.93% compared with control sample 1 when other relative humidity is 50%RH, and Under high humidity（90%RH）Its barrier property also improves 99.92% than control sample 1, during this is due to the present embodiment sandwich construction The excellent oxygen barrier layer of oxygen barrier property is introduced, and oxygen barrier layer is protected from humidity by vapor water barriers layer Influence, so as to effectively improve oxygen barrier property of the multilayer material under high and low relative humidities.So the present embodiment The sandwich construction of use can effectively improve material oxygen and water vapor barrier property, and barrier property is also notable to the stability of humidity Improve.

The mechanical property of table 2.

Meanwhile, the mechanical property of control sample and alternate multiple barrier material is as shown in upper table, and polycaprolactone is soft and tough, poly- second Enol is hard and crisp material.And the modulus of alternate multiple barrier material improves 89%, elongation at break compared with polycaprolactone 96% is improved compared with polyvinyl alcohol, alternate multiple barrier material being capable of being combined together the good mechanical properties of the two. This is due to the shearing of the multiple stratiform overlapping of layer multiplier, stretching action so that there is many in alternate multiple composite Interface, bed boundary compatibility is good, caking property strong, interface interaction power is big, is caused many according to stratiform equivalent superposition in parallel The caking property of layer composite is constantly lifted, so when being stretched by the external world, interface interaction enables to alternate multiple to hinder The mechanical property of barrier material is obviously improved；The shear tension effect in layer multiplier also causes dispersed phase, filler refinement in addition, There is more preferable caking property with matrix, while the strand of matrix has orientation effect and causes mechanical property is further comprehensive to improve.

Embodiment 4

The first step, Biodegradable high molecular base vapor water barriers layer（Hereinafter referred to as vapor water barriers layer）It is water from poly- PLA Vapor barrier layer matrix, myristin is vapor water barriers layer dispersed phase；Biodegradable high molecular base oxygen obstruction Layer（Hereinafter referred to as oxygen barrier layer）It is oxygen barrier layer matrix from polyvinyl alcohol, montmorillonite is oxygen barrier layer filler, is pressed Following components and parts by weight are got the raw materials ready：

Vapor water barriers layer component parts by weight

PLA (for vapor water barriers layer matrix) 92

Myristin (for vapor water barriers layer dispersed phase) 8

Oxygen barrier layer composition weight number

Polyvinyl alcohol (being oxygen barrier layer matrix) 85

Montmorillonite (being oxygen barrier layer filler) 15

Second step, is placed in 40 DEG C of vacuum drying ovens by myristin and dries 6 hours, PLA, polyvinyl alcohol, illiteracy are de- Soil is placed in 80 DEG C of vacuum drying ovens and dried 6 hours；

3rd step, the vapor water barriers layer material and oxygen barrier layer material of the drying that second step is obtained are respectively placed in high mixer Middle premixing 5 minutes, its rotating speed is 100 revs/min, respectively obtains the pre-composition of PLA and myristin（Water Vapor barrier layer pre-composition）And polyvinyl alcohol and the pre-composition of montmorillonite（Oxygen barrier layer pre-composition）, by vapor water barriers layer Pre-composition 40 DEG C of dryings 3 hours in vacuum drying oven, oxygen barrier layer pre-composition is dried 3 hours at 80 DEG C.

4th step, during the vapor water barriers layer pre-composition and oxygen barrier layer pre-composition that the 3rd step is obtained are dropped in respectively Squeezing by extruder A, B, junction station C, layer multiplier D the microbedding co-extruder constituted disclosed in state patent CN101439576A Go out in machine A and extruder B（See Fig. 1）, regulation extruder A and extruder B rotating ratio is 1:1, pre-composition is by extruder Charge door, transportation section, melt zone, homogenizing zone carry out fusion plastification, then two strands of melts is overlapped into initially by junction station C Structure, is molded, you can it is 129 to obtain total number of plies after the multiple stratiform overlapping of 4 layer multipliers by cooling tractor Layer, wherein vapor water barriers layer（Totally 65 layers）, oxygen barrier layer（Totally 64 layers）Wide 80mm, the thickness 1mm composite wood being alternately arranged Material（See Fig. 2）, the Thickness ratio of wherein vapor water barriers layer and oxygen barrier layer is 1:1.Wherein vapor water barriers layer extruder Charge door, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 80 DEG C, 120 DEG C, 150 DEG C, 170 DEG C, 190 DEG C；Oxygen The charge door of barrier layer extruder, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 190 DEG C, 210 DEG C, 220 DEG C, 230℃、230℃；The temperature of junction station and layer multiplier is respectively 230 DEG C and 230 DEG C.

It is above-mentioned many according to being put into after above-mentioned steps and parameter drying, high mixer mixing using above-mentioned vapor water barriers layer proportioning Separate unit extruder in layer co-extrusion device is extruded, but without junction station and layer multiplier, by with multi-layer co-extruded dress Put middle identical extrusion neck ring mold to be cooled and shaped, obtain wide 80mm, thickness 1mm control sample 1.The charging of wherein single extruder Mouth, transportation section, melt zone, homogenizing zone, the temperature of mouth mold are respectively 80 DEG C, 120 DEG C, 150 DEG C, 170 DEG C, 190 DEG C.

In above-mentioned preparation method, the control sample 1 of the present embodiment（Hereinafter referred to as control sample 1）Vapor water barriers performance in phase Humidity is risen to by 50%RH and only declines 22% after 90%RH, shows that its vapor water barriers performance has good stability to humidity change； But its oxygen permeability（For 1.7 E-14 cm³·cm/cm²·s·Pa）Than now, conventional packaging material polyvinylidene chloride is high Two orders of magnitude（Polyvinylidene chloride oxygen permeability is 0.057 E-14 cm³·cm/cm²·s·Pa）.Pair of the present embodiment Than sample 2（Hereinafter referred to as control sample 2）Oxygen barrier property under 50%RH relative humidity is good, but when relative humidity rises to Its oxygen barrier property reduction by 96.3% after 90%RH；And after relative humidity rises to 90%RH by 50%RH, vapor permeability By 0.7 E-14 gcm/cm²SPa rises to 30 E-14 gcm/cm²SPa, barrier property reduces 97.6%, Show that the barrier property of control sample 2 changes very sensitive to humidity, barrier property is badly damaged after relative humidity increase.

Vapor water barriers layer and oxygen barrier layer are effectively superimposed by the present embodiment using multi-layer co-extruded system, relative Humidity is risen to after 90%RH by 50%RH, and the vapor and oxygen permeability of embodiment 4 keep stable, vapor permeability by 2.8 E-14 g·cm/cm²SPa, which becomes, turns to 3.3 E-14 gcm/cm²SPa, increase only 0.5 E-14 g cm/cm²·s·Pa；Oxygen permeability is by 0.0030 E-14 cm³·cm/cm²SPa is changed to 0.0052 E-14 cm³·cm/cm²SPa, only rises 0.0022 cm³·cm/cm²·s·Pa.Compared with control sample 2, the resistance of embodiment 4 Separating performance is significantly improved to the stability of humidity, and this is due to that the vapor water barriers layer of outer layer can effectively completely cut off vapor and ooze Thoroughly, the oxygen barrier layer inside protection is not influenceed by vapor and humidity, is derived from good barrier property to humidity Stability.The oxygen barrier property of embodiment 4 improves 99.82% compared with control sample 1 when other relative humidity is 50%RH, and Under high humidity（90%RH）Its barrier property also improves 99.71% than control sample 1, during this is due to the present embodiment sandwich construction The excellent oxygen barrier layer of oxygen barrier property is introduced, and oxygen barrier layer is protected from humidity by vapor water barriers layer Influence, so as to effectively improve oxygen barrier property of the multilayer material under high and low relative humidities.So the present embodiment The sandwich construction of use can effectively improve material oxygen and water vapor barrier property, and barrier property is also notable to the stability of humidity Improve.

The mechanical property of table 2.

Meanwhile, the mechanical property of control sample and alternate multiple composite is as shown in upper table, and PLA and polyvinyl alcohol are Hard and crisp material.And the modulus of alternate multiple composite improves 24% compared with PLA, elongation at break and PLA Compared to improving 33%, alternate multiple composite being capable of being combined together the good mechanical properties of the two.This be due to The interaction of hydrogen bond of interface make it that the bonding of the two is close, and overlapped due to the multiple stratiform of layer multiplier shearing, Stretching action so that the presence at many interfaces in alternate multiple composite, according to stratiform equivalent superposition in parallel So that the caking property of multilayer materials is constantly lifted, so when receiving extraneous stretching, interface interaction enables to alternating The mechanical property of multilayer materials is obviously improved；The shear tension effect in layer multiplier also make it that dispersed phase is thin in addition Change, have more preferable caking property with matrix, while the strand of matrix has an orientation effect and causes mechanical property is further integrated to carry It is high.

Embodiment 5

The first step, Biodegradable high molecular base vapor water barriers layer（Hereinafter referred to as vapor water barriers layer）It is water from polycaprolactone Vapor barrier layer matrix, glyceryl tristearate is vapor water barriers layer dispersed phase；Biodegradable high molecular base oxygen barrier layer （Hereinafter referred to as oxygen barrier layer）From thermoplastic starch be oxygen barrier layer matrix, vermiculite be oxygen barrier layer filler, by with Lower component and part is got the raw materials ready：

Vapor water barriers layer component parts by weight

Polycaprolactone (for vapor water barriers layer matrix) 80

Glyceryl tristearate (for vapor water barriers layer dispersed phase) 20

Oxygen barrier layer composition weight number

Thermoplastic starch (being oxygen barrier layer matrix) 90

Vermiculite (being oxygen barrier layer filler) 10

Second step, is placed in 40 DEG C of vacuum drying ovens by polycaprolactone, glyceryl tristearate and dries 6 hours, thermoplastic starch, leech Stone is placed in 80 DEG C of vacuum drying ovens and dried 6 hours；

3rd step, the vapor water barriers layer material and oxygen barrier layer material of the drying that second step is obtained are respectively placed in high mixer Middle premixing 5 minutes, its rotating speed is 100 revs/min, respectively obtains the pre-composition of polycaprolactone and glyceryl tristearate（Water Vapor barrier layer pre-composition）And the pre-composition of thermoplastic starch and vermiculite（Oxygen barrier layer pre-composition）, by vapor water barriers layer Pre-composition 40 DEG C of dryings 3 hours in vacuum drying oven, oxygen barrier layer pre-composition is dried 3 hours at 80 DEG C.

In above-mentioned preparation method, the control sample 1 of the present embodiment（Hereinafter referred to as control sample 1）Vapor water barriers performance in phase Humidity is risen to by 50%RH and only declines 16% after 90%RH, shows that its vapor water barriers performance has good stability to humidity change； But its oxygen permeability（For 5.1 E-14 cm³·cm/cm²·s·Pa）Than now, conventional packaging material polyvinylidene chloride is high Two orders of magnitude（Polyvinylidene chloride oxygen permeability is 0.057 E-14 cm³·cm/cm²·s·Pa）.Pair of the present embodiment Than sample 2（Hereinafter referred to as control sample 2）Oxygen barrier property under 50%RH relative humidity is good, but when relative humidity rises to Its oxygen barrier property reduction by 78% after 90%RH；And after relative humidity rises to 90%RH by 50%RH, vapor permeability is by 3 E-14 g·cm/cm²SPa rises to 25 E-14 gcm/cm²SPa, barrier property reduces 88%, shows contrast The barrier property of sample 2 changes very sensitive to humidity, and barrier property is badly damaged after relative humidity increase.

Vapor water barriers layer and oxygen barrier layer are effectively superimposed by the present embodiment using multi-layer co-extruded system, relative Humidity is risen to after 90%RH by 50%RH, and the vapor and oxygen permeability of embodiment 5 keep stable, and vapor permeability is by 4 E-14 g·cm/cm²SPa, which becomes, turns to 11 E-14 gcm/cm²SPa, increase only 6 E-14 gcm/cm²· s·Pa；Oxygen permeability is by 0.09 E-14 cm³·cm/cm²SPa is changed to 0.12 E-14 cm³·cm/cm²·s· Pa, only rises 0.03 cm³·cm/cm²·s·Pa.Compared with control sample 2, the stabilization of the barrier property of embodiment 5 to humidity Property significantly improve, this is due to that the vapor water barriers layer of outer layer can effectively completely cut off vapor permeation, the oxygen blocking inside protection Interlayer is not influenceed by vapor and humidity, is derived from stability of the good barrier property to humidity.Other relative humidity The oxygen barrier property of embodiment 5 improves 98.2% compared with control sample 1 during for 50%RH, and under high humidity conditions（90%RH） Its barrier property also improves 98.2% than control sample 1, and this is due to that to introduce oxygen barrier property in the present embodiment sandwich construction excellent Good oxygen barrier layer, and oxygen barrier layer by vapor water barriers layer the humidity that is protected from influenceed, so as to effectively carry Oxygen barrier property of the high multilayer material under high and low relative humidities.So the sandwich construction that the present embodiment is used can have Effect improves material oxygen and water vapor barrier property, and barrier property is also significantly improved to the stability of humidity.

The mechanical property of table 2.

Meanwhile, the mechanical property of control sample and alternate multiple barrier material is as shown in upper table, and polycaprolactone is soft and tough, thermoplastic Property starch be hard and crisp material.And the modulus of alternate multiple barrier material improves 73%, extension at break compared with polycaprolactone Rate improves 97% compared with thermoplastic starch, and alternate multiple barrier material can exist the combination of the good mechanical properties of the two Together.This is due to the shearing of the multiple stratiform overlapping of layer multiplier, stretching action so that existed in alternate multiple composite Many interfaces, bed boundary compatibility is good, caking property strong, interface interaction power is big, is made according to stratiform equivalent superposition in parallel The caking property for obtaining multilayer materials is constantly lifted, so when being stretched by the external world, interface interaction enables to alternately many The mechanical property of layer barrier material is obviously improved；The shear tension effect in layer multiplier also causes dispersed phase, filler in addition Refinement, have more preferable caking property with matrix, while the strand of matrix have orientation effect and so that mechanical property is further integrated Improve.

Claims

1. a kind of alternating stratiform Biodegradable high molecular barrier material for having excellent vapor and oxygen barrier property concurrently of preparing Method, it is characterised in that the barrier material is by Biodegradable high molecular base vapor water barriers layer material and Biodegradable high molecular base Oxygen barrier layer material is respectively through fusion plastification, and the coextrusion system being combined by two extruderses is being designed to 3 runners Overlapping is obtained after the initial configuration of 3 layers of parallel arrangement in junction station, then is entered by n layer multiplier being connected with the junction station Row stratiform is overlapped, and being formed, there is Biodegradable high molecular base vapor water barriers layer and Biodegradable high molecular base oxygen barrier layer to hand over For the sandwich construction extrudate of arrangement：

2. preparation according to claim 1 has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable high The method of molecule barrier material, it is characterised in that the matrix of described Biodegradable high molecular base vapor water barriers layer, which is selected from, gathers oneself One in lactone, PLA, poly-succinic fourth diester, polyhydroxyalkanoate, PHBV Kind；The dispersed phase of vapor water barriers layer is selected from glyceryl tristearate, laurin, single nutmeg acid glyceride, three meat One kind in myristin, tripalmitin.

3. the preparation according to claim 1,2 has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable The method of macromolecule barrier material, it is characterised in that the parent of the dispersed phase of described Biodegradable high molecular base vapor water barriers layer Water contact angle is higher more than 30 ° than the hydrophilic contact angle of the matrix of vapor water barriers layer.

4. preparation according to claim 1 has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable high The method of molecule barrier material, it is characterised in that the matrix of described Biodegradable high molecular base oxygen barrier layer is selected from polyethylene One kind in alcohol, thermoplastic starch, thermoplasticity soybean protein isolate；The filler of oxygen barrier layer is selected from montmorillonite, graphene, leech One kind in stone, zeolite.

5. preparation according to claim 1 has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable high The method of molecule barrier material, it is characterised in that the sandwich construction extrudate is by by two extruderses（A、B）, junction station （C）, n layer multiplier（D）, shaping mouth mold（E）And cooling tractor（F）The multilayer extrusion system melt extrusion of composition is simultaneously cold But sizing is obtained；Its vapor water barriers performance and oxygen barrier property can be by the gross thickness of sandwich construction extrudate, internal total The Thickness ratio regulation and control of the number of plies, vapor water barriers layer and oxygen barrier layer.

6. the preparation according to claim 1,5 has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable The method of macromolecule barrier material, it is characterised in that described sandwich construction extrudate gross thickness is 0.01-10mm；Sandwich construction The total number of plies in inside of extrudate is 3-32769；The thickness ratio of biodegradable vapor water barriers layer and biodegradable oxygen barrier layer For 1:99-99:1.

7. preparation according to claim 1 has excellent vapor concurrently and the alternating stratiform of oxygen barrier property is biodegradable high The method of molecule barrier material, it is characterised in that 3 layers of initial configuration of described sandwich construction extrudate are that two outer layers are water Vapor barrier layer, intermediate layer is oxygen barrier layer, and when using n layer multiplier, material hinders in two layers of outermost for vapor Interlayer, and the vapor water barriers layer structure being arranged alternately parallel with oxygen barrier layer, the total number of plies of material is 2^（n+1）+ 1 layer, wherein, n For 0-14.